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E.' M.10HANSEN. METHOD 0F TREAKTING OIL. APPHCATION FILED MAY 9, 1919.

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SQ kw@ NQ E. NI. JOHANSEN.

METHOD 0F TRETING-OIL.

APmlcAloN FILED MAY9,1919.

Patented Dec. 12, 1922.

7 SHEETS-SHEET 2.

E. M.10HANSEN. u METHOD OF TBEATING OIL. APPLICATION IILED MAY 9, 1919-Patented B66121922.

7 SHEETS-SHEET 3.

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E. M.10HANSEN.

METHOD 0F TREATING OIL. APPIICATION'HLED MAY 9,1919.

E. IVI. JOHANSEN.

METHOD 0F THEATING OIL. APPHcATloN FILED MAY 9, 1919.

E. M`. JOHANSEN.

METHOD 0F TREATING OIL. AmlcATloN FILED MAY9,1919.

-WNLN ERNs-'r ivi. QioHANsEN; or 1Dieriizlinniirii'LA,v rENNsYLvliNIA,issreNoifiy fro ,THE

e'rLAN'ricNErrNiNe COMPANY, or rriinannnrnin, rNNNsYLvANInAconT,

` Poiin'rioN or PNNNsYLVANInQ;

l np'piieatiorimed Mayke, i919. 4semi No. vfzeeie.`

Be it known thet, ERNST lvl; JOHANSEN, a citizen of the" United States,residing 4- in 'the city und county fof 'Philadelphia7 'State *ofPennsylvania have. `invented lcertain `new and i.isefulj fniprovenieiits"in \Methods y 0 1' Treating` Oil, of Which the following is aspecifications, i i f c My invention `relates to the-treatment 'ofpetroleuimpshaleoil or other inineral loils and oilsderivedifroinyniineral depositsgles coal7 for improving i'eiii'i'eryrprocesses and for prociiringriniproved products. n j

My invention resides'in e method of treating` oils `of the characterreferred tofor re` movingtherefrom solids in suspension or in colloidalstate or forno, roi other lineterials,'

naturally existing inthe oil or resulting from treatiiient thereof,whichl have"` intern fered with refinery processes oi."\vliose pres!encc prohaiiily heretofore unrecognisiedyhas entailed certain refineryprocesses in attainn ing; certain products.

lilly invention fresidesinore particularly a` method of tren-ting oilsofthe 'character ahove referred to andespecielly lubricating fdistillates or stoclssfor renderingl the sanievnon-einulsifving' or of*a character With- My invention vresides `further in "a method* oftreating oils ofthe character vYahir-,Je `referredto, andrespeciellylubricating distillates or stoclis'either before or after,` or hoth`before rind aftertlieecid treatment., such as'i treatment bystrongj'rsulphuric acid', with resultant advantages inthe and in theproducts-- ending of Sonie i of the veri* ous incr es ofprocediireicoinpiehended" With-y in my inventioiny reference may he yhad tor f theconipan'ving' drawings? in `which in ous inodesof tion with which nFin'. is ache, ccdure in classifying oils.L n l l Figs'oand (3j arerespectively, charts ,of possible inodes of procedure for determiningthe quantity'of soep lsind dilution of soap solutionfor Washing a classoihy pet'r'oleuinin connecyinvention is available.

refining'processes l l' non-emulsifying it isdesirslole' toreniove theeinulsification-inducing solids 'therein`r andtliis in accordance withone feature `of` 5 t of possible inode of pro- I 7,18 and 9 -are,resp,ectively, charts of possible modes(A of procedure. indetermining respecting a class 3 oil the quantityof Yalkaliv to be usedinthe'first stagewasliiiig, dillision of soapsolution in first stageWashingfand" the second stagetrezitinentf .Respecting the cause ofemulsiii'cation of V oil off-#the character referred to lwith Water, l

4from theoretical considerations and from" practice I afin led tobelievethat permanentvv emulsionsv of the oilv with Watery aredue to thepresence in the oil or Water of solids in nelydivided stateinsuspension, or solids in colloidal fo'iin or state, as distinguishedfrom solids -present in true solution, in Which" lest case the solids donot induce emulsificw tion. rllhese solids to he reinoved'probablyinclude asphaltic bodies `lpolyineiizati,onf

products, iniiieraland vother finelyr divided bodies. With such solidspresent inthe oil or Water when the oil and Water are-agitated to causea fine subdivision of one,r the vdis- "perse'd phase, in the -otherythecontinuous phase7 the solids referred to areadsorhed et the interfacebetween the oil andy Water,k

and are present in the continuous'phesetthev strengthen the films of thecontinuous phase tosuch extentl that 'they cannot loebroken hv the`interfacial tension between the oil and Water, and so a permanentemulsion rv'villfresult. While the filnis of the continuous phase, asoil, betweenthe particlesof the dispersed phase, vas Waterfare thusStrength 'enefl'hyr the idsorbed solids, lthe interfacial tensionis atthe ysaine time decreased" bythe if presence of these solids and lisaccordingly unable to rupture the strengthened iihns of. ythecontinuousphase, so preventing coales# kceiice` and separation ofthetwoliojuids.

To render an `oil having such solidsy lthereniy..-invention'is brought iabout by causing To' this endl employ' ay suitable liquid,` as asolution of suitable soap in Water, which has an interfacial tensiontowards the sol-ids'in the oil lower than the interfacial'tensionhetween'the oil `andthe suspended or colloidalr solids which are to be.removed; or, otherwise stated, I employ a liquid Which Wets the solidsmore readily than does the oil in which they are present.

Removal of the solids from the oilA to produce a non-emulsifying oil bythe aid of another liquid, as a suitable solution in Water, may best becarried out by causing the solution to become dispersed in the oil,since this is the condition under Which the subsequent desired completeseparation of the oil and treating liquid will most readily take place.

In accordance with my invention, there fore, I produce a non-emulsityingoil or otherwise beneficially atleet an oil by Washing it With a Watersolution of suitable substance, as soap, causing the solids te migrateromthe oil into the solution, care being' taken to employ soap ofsuitable character Whose total amount is suthcient to operate upon thequantity or solids present in the oil and to regulate or control theconcentration or dilution ot the soap solution.

Referring to Fig. l, there is shown in chart form an ordinary fractionaldistillation of petroleum, for. example rlppalachian crude oil,resulting in various cuts indicated, of which the rening ot the Wai;bearing distillate and'oil residue is more or less fully indicated, inwhich my method of oil Washing may be employed to advantage.

InFig. 2 there is shown in chart form a possible inode ol' refining'crude petroleum by cracking distillation. ln this instance the refiningof resulting Wax bearing distillate is shown more or less completely, mymethod oit washing; oil being of advantage therein.

In Fia'. 3 there is indicated in chart iorm a possible mode oldistillation et' crude petroleum, as mid-continent crude, involvingtopping orproduction of a reduced crude oil Whose refining; is indicatedmore or less completely and in which my method of oil WashingV is ofadvantage.

In Figs. l, 2 and 3 the stage at which my method ot Washing may bepracticed is indicated by the Word "Nash. Besides the Washing,`indicated in refining Wax bearing distillate, oil residue and reducedcrude oil, it will bc understood, as indicated in Tfigs. l to 3inclusive, that gas oil may be Washed in accordance With my invention toproduce an improved marketable Anjas or fuel oil product, or which maybe subjected to further refinery treatment, as cracking' or crackingdistillation for producin@ lighter hydrocar` bons, including, gasolene,or for any other suitable purposes.

Inl? l the Washing will `be found, .'especting the WaX bearingdistillate, as an alternative to acid treatmentot lubricating stoer,Washing being resorted toV prior to acidk treatingT the oil *from whichresults a sour oil which is neutralized and Washed in accordance With myinvention. And in the Lassie@ xfs tralization ot resultant sour oil.

l'lespecting the oil residue, Fig. l, Washing may be practiced, as analternative to acid treating, prior to acid treatment, the sour oi troniwhich may then be neutralized and washed in accordance with myinvention. Gr Where acid treatment oi the oil residue is practiced, thesour oil is neutralized and Washed.

In trie relining' method indicated in Fig. 2, my invention may bepracticed in connection with the rei'inement ot ivan bearing distillatepractically the same stages and in the same vfays as indicated in Fig.l.

ln trie mode of refining indicated in Fig. 3, the crude petroleum is rsttopped b y sub- `iectiv ,33 it to steam blown therethrough While heatedby tire in a still to remove light hyrocarbons, as gasolcne, etc.,indicated as crude naphtha. rlhe topped or reduced crude oil is thentreated as indi-cated, and the wat; bea distillate and eil residue,resulting` iro-m fractional distillation ot' the neutralized sour oil,are then treated substantially as indicated in l in connection with theWax bearing distillate and oil residue thereof, my Washing' processbeing' available and Where indicated.

iinong the materials suitable to be used in conjunction with Water JlorWashing oils of the charact referred to in accordance with my inver. n,are in general substances which vfill loiver the surface tension olWater to suitable extent, such as resinates or resin soaps, soags etfatty acids, including ordinary domestic or laundry soaps, naplithenicsoaps, soaps, including those derived from milk` water, oi: Organic, assultonic, acids resulting1 from treatment of oils ujf; stron;V or

L) turning` sulphuric acid and 'found both'inthe separated sour oil andin the acid sludge; these Water soluble soaps are those of the alkalimetals and ammonium.

For forming` any of the suitable soaps util ized in my method, andespecially for tormins soaps by reaction with organic acids contained inthe oil, there may he emgloyed as suitable sodium, potassium or ammoniumhydroxides, or in lieu of' hydroxides of these metals, thei" carbonates,bicarbonates or equivalents may be employed.

In general, the oil to be washed is agitated in any suitcble Way, asmechanically orfbv blowing' aii herethrough,vinile the nsame ismaintained at suitably high temperature.

The temirierature of the mixture durimr treatment is aendent upon theviscosity of the oil. it beine' understood that an oil of hich viscositywill be 'treated at hipgh temperature. he object is to secure suitablefluidity of the oil and accordingly with higher viscosity highervtemperature is employed,

somewhat below 212 rdegrees F. inthe eases of oils of VeryhighViscosity,V While agitat` ing-the oily at suitable temperatuiejwaterisfy present oradded insufficient quantity, the j matter of dilution in'thewashing operation benigni? importance in that there must loe presentsucient Water tofreceive trom the mixture 'the lsoaps and the solidparticles orf material Washed/trom thev oil, andyet the Watershouldnotbey present in,k such excess as to reduce the `cyoiicei'itration ofthe-'soap fto such point that it is no longer ablev suitably to Wet thesolid `particles to Abereinoved from the oil. Norshould*ther-concentration tot soap solution be so great as to .causeemulsifiicatioii of the oil Which it is desired'to lWash;

In Washing kan acid treated' oil, particu-` lailyy torproducingnoneinulsiying oil, the

quantity oic soap involvedy as Wellj as its concentration kor theyquantity of Wateriiivolved rare of importance in that sutlicient soapshould be present with ii'eg'ardito the amount yotlsolids orother'materials to be `Washed from the oil, andthe quantity of WaterHor, dilution is of importance to reffect interi'. ,ial

tension suitableor proper for migration of,` lsfij'rom thoril `my methodor process of oil Washing,- a suit?.

able quantity of soap is necessary, dependent uponthe' quantityot-solids or-other material to be removed; that. they amount of Awateror dilution .istot importance, andr "tliatsuit-l able temperaturesandagitation are-also de-k sirable. I f i y i, o The treatment orfwashingof. the oilin accordance with my inventioiimay .be either before an acid,treat-mena after-Lucid treat-- mentjor both before and afteracid'treat-v ment.

As to the Washingn or treatment 'sotoils which have. first undergoneAso-called acid y treatment by strongsulphuric acid, torexy ample, 66degreesB. or stronger, including turning sour oil, which is the oilWhichhas been separated from the resultinig` acid sludge and contains tracesy.of` suspendedinineralacid and dissolved 'organic soap-forming acids,

may in general coiitaiii'either too small ani amount of organic.soapioriningfacida a y excessyoi soap-rormiiigi suiicient amount oisuchacids or an excess oit' such acids, ythe three classes requiring'treatment of ,ditliereiity characters oit' ytreatment; v

suitabley inode of determinationofthe lclass `to which belongs avsouroil'is indicated iii d., The oil, which may be,"

for example, a lubricating stock@ is acid treated and then separatedintoacid sludge vand sour oil. v The class to' which thisy sour 'toclass l.'n A.

n When the dispersion upon standing,` sepasulphuric acid, I have ltoundthat the soap-forming acids Which when neutral' "case Ln-emulsionnii'scil'i'ler uitJ` added thereto, or it it .oily belongs, is thendetermined in the following Way. A sampleot the sour oil is titiated foracidity causedl by both mineral andv on ganic acids. A' new sample oithesour oil is then taken and "there is added thereto a slight excess ot'`suitable reagent,y for exam- Y' ple, a sli ght excess of lf/2)' aqueoussolution oit" caustic soda. f l. n Theiiiixtuie is agitated While ithereto. yThe agitation, dilution and heating .of the mixture isciectedvin anyfsuitahle Way, but prei'erably by passing steam there-kthrough,` as for example, tor one-halt houi` f orjlonger, and untilanarbitrary amount oi Wateigkincluding the Water containing the reagent,has vbeen added, Ytor exainple,l30%

`lvl/ienv agil tation-is discontinued the 'mixture isa disot thev Volumeof the sour oil.

persion of oil and `Water, and the behavior of this dispersion is tlienobserved. lt. may

"not separate vat all, inuihich case it is an emulsion which is notiniscible with Water When added 'to Water, sincethe LWater is in 1 thedispersed phase andthe 'oil is the continuousophase. 0r it mayseparate-in two `characteristic Ways, ifirst, into a layer of emulsionWhose Volume is greater7 than. thc.r volume ot the sour oil and which isnotA inisciblewvith water 1when added'to Water. and alower layer oiaqueous solution; or,

the emulsion. and oil `layers beinpf greater thaiithe volume of the souroil, il disperlpt at tem-V perature suitable tor reduction oit the viscosity ,of the oil, and ydilution Water added;

sion behavingn in any oiierot' these three Ways,

indicates that inthe sour oil tl re are not yenough soajp-ormiiigvorganic acids to form upon neutralization suiiicient ysoap effectivelyto WashV theoil, by removing vtheretrom `solids or other inaterials.xsuch those inducing emulsiiication,y and the voil belongs affordsuiiicieiit soagfor elise-tively, was tlie'oil. n f i n The oil belongsto class one harina an ls tl ir the disiiersion aile to it l A l ytrates into layer o'l" oil Whose roluiiic is much less than the Volumeof the sour oil sunnite, and-into `a layer oi emulsion misrihle withWater when 'added thereto. `lhesc emulsionsmiscible with Water Whenadded thereto .have the oil dispersed inthe continuous phaseot Water,

iii such" 1 atei`r lwhen.

iso

this being a reversal ot phase as compared to the above mentionedemulsions which not miscible T',vith Water when added thereto.

To an oil of class 1, Where the soap-forming organic acids inthe souroil vare too small in quantity for forming upon neutralization oi thesour oil with hydroxide or equivalent solution the requisite amount ofsoap essential to removal ot the amount of solids or removable materialpresent, l add either soap-forming organic acids, either before or theoil is acid treated, or soaps as such. nn adding soap-forming organicacids a su icient quanti" is employed which.

with the soap-Forming organic acids present case the added soaps withthose produced by neutrlizino' the organic acids in the sour oil aresutlicient to remove the particular quantity of solids present.

The amount orn soap-'forming organic acids or the amount of soap such tobe added to an oil et class 1 may readily be found by determination or"the total quantity of soap necessary s .bly to Wash the oil. rind thistotal qu nity ot soap be determined in any suitable Way. one example ofwhich is illustrated by the chart in Fig. 5. Any suitable number ofsamples of' the sour oil, as 5. is taken, and to each sample is addedsuitable reagent, as

aqueous solution ot caustic soda or equivalent, in amount slightly inexcess of that previously determined by titration as requisite 'forneutralization ot the sour oil. For example, a slight excess oit 4%solution or" caustic soda may be employed. Through each oi' the tivemixtures is passed steam in the presence oit diilierent amounts of soapin the different samples, the agitation being continued a suitablelength ot time and until an a bitrary dilution, 30%, is attained. Thetive samples are then allowed to stand andtheir behaviors as toseparation noted. For example, 'to the tive different samples may beadded` respectively, 0.2%, 0.4%, 0.6%, 0.8% and 1% of soap by Weight pervolume ot sour oil, as grams olx soap per litre of oil. The separationsbe ot the 'character indicated in Fig'. 5. trom which it into clear oiland milkA Water being thede-` ciding factor, it is seen that the samplecontaining 0.6% of soap is the one so separating and containing theleast soap. Accordingly, in treating the oil on a large scale in theplant, its contained acid is' neutralized by sodium hydroxide orequivalent and there Will be added thereto approximately 0.6% ot soap.Or in lieu of adding soap as such, there is added to the oil organicsoapforming acids of quantity sutlicient to produce upon neutralizationan amount of soap equivalent tothe soap added as suoli.

The extent of dilution or quantity of Water to be employed should.however` be determined. This may be accomplished in any suitable Way,for example, by the mode of procedure indicated by the chart in Fig.` 6;To any suitable number of samples,- Jfor example 4, of sour oil is addeda slight excess o'l" reagent, for example. a slight excess o 4% aqueoussolution ot caustic soda. Through vach sample is passed steam in thepresenceo't 0.6% to 0.8% of soap, as indicated by the chart ot Fig. 5,continuing the agitation until various dilutions ranging, for example,from 80% to 60% for theA different samples, are attained. The behaviorot the different samplesl as to separation is` then observed. Asindicated in Fig. 6, both thc samples diluted to 30% and 40% separateinto clear oil and millr Water. In consequence. Lf-0% is taken as themaximum dilution. The other dilutions of 50% and 60% separate intolayers one of which is an emulsion, in addition to the milk Water ormilxy aqueous solution, the formationot emulsion indicating that the 50and 60% dilutions are excessive. In the case the dilution is too small,as for exan'iple using materially less than 30% dilution in the exampleo 6, the dispersion separates relatively sharply, but the upper oilylayer is lgenerally more or less cloudy.

Accordingly in the `plant on large scale the agitation ot the oil willbe eiected at suitable temperature in the presence ot say, ll0% dilutionWater, The Water containing the necessary reagent, or soap and reagent,is included' in the 40% dilution.

llllhen an oil is in class one containing suiticient organic acids toform the suitable or requisite amount of soaps, the Washing is eected byagitating the oil at suitable temperature in the presence of aqueoussolution of sodium hydroxide or equivalent' in amount slightly in excess01"' that necessary to neutralize the acids present in the oil. Butsuitable dilution should be observed, and this is determined in anysuitable Way, as by the method indicated in the chart of Fig, 6.

1n the cases of both class 1 and class 2 oils, after they are Washed asdescribed, they `are allowed to settle, the oil separating as a clearsuperi/Latent layer which` should be non-einulsitying,V sin-eetheernulsifination-in-` ducing agentsfhave been removed ly the treatment.they separation will be found variable conditions depending; uponthenaturey ofthe oil and thenature of its treatment. In general, the loiveraqueous solution will he` milk Water, an emulsion with Water ci' a smalltractionv ofthe oil and,the'solidsr'e-k moved therefrom While 1nrsuspension or in colloidal state, the soapsholding` the ce moved solidsand the oil in the state oit Y,

emulsion. The emulsion may be broken in any suitable Way,v as rbyaddition ol dilute rnineralacidor suitable salt of: a mineral acid,lwhereupon there is a separation of the inillr Waterjintolayers one oli'which isthe oil with the'soaps or soaporrning acidsin solu'tiontherein,together with the removed solids; and a lovver ylayer or Water contain'infr the vmineral acid ormineral'acid salts.

The crude upper or oily layer such.

be used as a soapy or soap-forming material in the oilvvashing'processes hereindescrlbedg-or `r'by removal of thesolids a more refinedsoapy'or vsoapi'n'inine; material isavailable 'for 'my oil'ivashingnriethod. Fronii the lirst mentioned oily layer have sepa-` ylargeamounts 'of naphthenic acids vpresent in the original `or "crude oil, atwofstage lvvashing is Lresorted to. "ln the first stage only part' ofthe organic acids are Washing', y neutralized to forni soaps, the`nurture Abeing agltatedcat suitable temperature inthe `presencectsuitable ainount` of .dilution Water. This iirst stageWashingreinovesall;

or a. large part of the ,solids or other linate- -rials vintol theWater, leavingin the oil un-1- neutraliaed Vo'reganic acids.- ln' theaccompanyine` mill; water troni which the oil separates, is n emulsion'oi'v a: small'trac@ tion oi theciland allora lznjge portionoi2 thesolids `which itis intended shall be renioved together with soap inamount .cor-F responding tov the .amount of organic acids neutralizedAliter'removing thefoil fr-oni the aqueous layer or milkfyvaterit is"subjected to secondy ystage Washingwhich in general is ythe saine asthat for 'a class 2 oil as above described; nainely7 afncutralif Zationwith sodiumfhydroxide or'equivalent solution o j`V theremaining-organic' acids which/form sulicient soapto-frernovefany lnthelower aqueous layer ol" solids or other removable inaterials'rreinainfing-in the oil, "llfall the solids are removed intheiirststagev\7a"s,hin g, the second stage washing is'merely one ofy'neutralization 'of the remaining organicl acids toy i'ornil soapsWhichgo into solution in-the added Water, the mixture' separating with alayer of clear non-e1nulsiying oil.v

The determination "of the 'quantity of alkalior reagent to beadded to aclass 3 oil *for the firststage Washing ort'rea'tnient niayfbe by anysuitable methody'as dor eirainple, that indicated by' the chart in Fig.7.

To each of any suitable number ot samples of the sour oil, for example35 is added a different 'quantityffo'f reagent of suitable strength, forexample; of l% `aqueous solution of caustic soda, but veach of thesequantities `is less than the quantity of 'reagent necessary to'neutralize the'sou'r oil- Through each sample steam is passed untileach has attained a r30% dilutionT i Upon' standing, the behavior of thesainples is observed.' "For example', to the three samples of oilv maylvhe added' respe'ctively,` 50% andl75 70 of `=the reagent necessarycompletely to neu-v tralize `'the acids in the lsour jo'il@ *Asindicated34 ther saniples containingv respectively 25 721 and 50% of the4reafgent necessary for heutralization,l may separateinto layers-oi yclearoiland niillr Water-or niillr-y aqueous' solutions. These 'are"bothf suitable or desirable`cha1acters oiseparation;v but `the 50%additionfol" reagent isftalren'vas giving the yheet results7since'itl'sthe 1naX'nnuniy of the twoquantities vwhich Will vpr'o'chice'a separation of clear oil; leaving less'acids tofbc'neu `tralized in thesecond stagewashing. The

sanipleftofivhichjhas'bcen added?? of the f 'quantity of reagentnecessaryto neutralize it"`1i iay`;lorni"an emulsion; and accordingly noseparation takes place. This is undesir- "ableQ-sinceif the oil'be-sotreatedfthe Idesired i e] Washing isl defeated byfforination offeniul'-sion. f i "Having deterniinedfthe 'suitable'pe centage of reagenti to'be added thel 'd ilutio'n n`iay he determined by any suitable methodfor' example' that `indicated "bythe Vchart o .ien 8.# To eachoianysuitable VI nirnber of ples of the sourjoil.` for example 4? l isadded enough oli, say,A a4% caustic'y soda solution to neutralize 50% ofthe acids presenta this ypercen tagehaving'been determined rby thernethodV .indicated in Fimf `llhrouggh veach continuing to* difi 1sample is passed steam',

vferent dilutionsj :For the different `Asarnples.

The behavior yof "the samples upon 'discontinu'ati'o'n of 'agitation isthen observed.

dilutionfissatisifactory the higher dilution generallybeingtaken.ylWVhenv the mixture separates Linto anfupperlayer of oil; anim eil Saim-When the dispersion" separatesinto llayer "y oi clear oil and' a layerofmilkrfrvater;` they terniediate f layer of emulsion y. and a .lowerlayer- 4 of milk Water-for milky aqueous-solution, the dilutionhas been.too great. The dilutionsfor the different samplesniay be, for example,ras indicated` in Fig. 8, respectively 30%, 40%, 50% and 60%. The'highest -dili-ltionwithout rproduction of -a layer of emulsion ischosen. In the example illus- Itrated `itis a 50% dilution. f Thedispersion separates into-a layer of oil,\designated A, anda `layer of'milk water. The oil TA 'is drawn ofi' from the milk water and is theoil 4which is then subj ectedI to the second stage Washing.

The' secondsta'ge treatmentor Washing may be of any 1 suitablecharacter, for example, that indicatedin therchart :of {Fig-,9. .Asample of l the o il Af Fig.l `8, .is, .ti trated to @termine there Yequivalentinecessary. to neutr lize the:. acids A rerna'ining? therein.This .isi in' etlect, how-- evenvknownsince f inthe method indicated'in fFg. 8-`50 @only .of the `acids present. in .theorignal oil'havebeentneutralized. This inea'nsthat the oil still contains v50% `of theoriginale-mount ofacids. There is Ithen added to the-salnpleaan Yaqueoussolut-ionot caustic wsoda or equivalent, 'for example, 4% aqueous-solutionof"caustic i-soda, in Vamount slightlyv inyencess of thatnecessary -to Ynenitral-ize the; acids remaining `ini the oil A; Steamis I then passed therethrough i to agitate' ythe same and toefltectz4 adilution of, s ay, 3Q%. TheV dispersion isthen allowed -tojgstandvand-fsepartes into a layer. of milk Water O11 m .ltrv'fx-011.1601143solution.. and ezSu- `pernat'ent layer of .cleatrnon-emulsifyin'g oil. Y Obviou"s ly,el'these methods 'indicated in Figs,7,.8 and-9garefthen readily reproducable inthe plant -on large batchesVof class 3 foil'. A 4 h'ile the foregoing ni'ethofds of washing o'ilsothethree classes areaVai-lable in connection With various mineraloils, acid treatedstocks 'for lubricating'oil's, from lboth asphalticandnon-a'sphalticlcrudepoils, 'will -be foundyto fall in Vany one-offthelfthree classes, and so-c'alled fstearnitest, or vnon-emulsiiying lubricating foils `.may be produced byiapplying the; suitable--,one of the .three modes of T'treatinent or IWashifng fabove.de- -scribed. v Treatment rotan acid' treatedoilasabcve describedimproves its sparkle -.or color' and reinoves. o`dor. Then undergoingthe -socalledfcarbonetesn as usually applied yto Van `oileandAparticul'arlyto af-lubricating' oil,vleSs fixed carbon-is found-@intheoilif treated-or Washed as'above.( lescribed. A

While: as'to 1 the oils-separatinfg.v from the a d mi? V.1intreatment@tithe-three boveidesribedetheirclarity Vay lyajrgfelynbefdependedifupon- :Sin

.liess-,764

making` determinations or arriving: at desired results, it Will beunderstood that such observations may be supplemented by steam test orother usual tests ot the separated 'clear oils to determine'whether ornot they are Otan emulsitying character; or steam or other tests may berelied on to the exclusion otinspectien of clarity or color.

Respecting` dilution` it ma;7 be stated in general, though Withoutlimitingr my invern tion thereto, that it will seldom exceed 700.5; otthe volume of the sour oil, the percentage ot dilution Water including'not only 'the Water added, but in addition, the Water containing thereagent.

l have toundit ot advantage te Wash an voil of character requiring' acidtreatment or filtration before such acid treatment or {iltratien 'bysoap or equivalent solution offtlie general character hereinbetoredescribed.

Such washing before acid treatment may comprise any ot the modes ofWashingthe three 'classes ot oils as above described in connection withacid treated oils. lhere the oilis in effect a class l oil, one hay/lpginH suilicient organic acids to form sufficient soap to accomplishsatisfactoryT Washing', suitable Iquantity oit organic acids may beadded thereto and then neutralization effected to procure the necessaryamount ot soap with Which it is then Washed. oil may belong' in classi2, in which ease tralization will produce sufficient Vsoap 'ttor theWashing treatment. l nd iff' the'oil conv talns excessive amount oit nicVsoapferming acids, it ma be tre.. ted by the double stage Washinghereinbe'tore described, though it Will be understood that it willrarely, if ever, happen that an oil Whichhes not been acid treated willtall .an 3.

.lngenerah however., a solutien containing suiiicient soapand ofsuitable dilution is' agitated `with the oilv'to Wash it before acidtreatment, or the soep may be formed by neutralization with sodiumli'ydoI-:ide or equivalent ot organic acids contained in the oil beforeacid'treatment. In any event, the Washing is ot the general' characterdescribed and effects several important advantages. One et these is thetactthat materially less otstrc sulpliuric acid necessary to'acid treathe Washed oil. the saving beingginsome instances as great as 05,3 andbecauseles's acid ernployeddn treating' the oil, less of theyaluablehigh risc constituents of `the oil .are aitected ci eyed by the acid,with the result that the acid treated oil, after removal of the acidsludge therefrom, will be found to be ot materially higher viscositythan if the Washingpreceding the acid treatment 'Were not resorted to.Theoil resulting from neutralization othe seurfoilPis of better sparkle,transparencyor color than. in the ycase `.ir'fhere the Washing llO[preceding acid treatment is omitted.V The quality of 'the acidsludge-resulting;'from the I acid treatment oi theoil following theabove described Washing-With soapis improved in sludge yieldssultonic'acidsyas of Taveau' Patentillo. 1,27 17387 5 which are morekconcentrated or purerthan otherwiseattainable.L

The acidsludg'ey settlesmorey readily or rap- .idly from the acidtreatedbil than inthe case Where the omittedyy e n i l A furtheradvantage-due to the'washing preceding vacid'-treatment isza saving inthe step kof previous Washing* is `volume of the oil treated; yas oneexample,

Where I.Without previousy Washing the loss in Volume ofthe oilbyacid-treatment` is vabout 18%,' by f previous rWashing the loss` mayybe i `reducedto about 11%.

,v Following. the acid :treatment of the, previously Washed oil the souroil is usual kneutralized with sodium hydroxide or other suity ableorequivalent solution; generally speaky ing, Washing" oi the oilprevious to thefacid trea'tinenttyields a :sour oilwhicli lWillby the`usual neutralizationwith` sodium hydroi de `orA equivalent produce ainon -emulsiiying oil. ln some cases, Vit may be .desirable to add acidsor soaps, asy treatedoils. y Y I f y l l'The vabove broadlyl'describedWashing of `oilloeiore acid treatment, aswell as before and 4after aciditreatment, lapplies also to stocksA -for, producing' lubricating' oils;from in thek case/of class l acid as indicated inllligs. l, 2 andIB. .f

vThe character o'fkwashing. or treatment of an'oilbefore ithas ,beenyacidtreated may be ,determined 'asin the case ol? a *souroil ashereinbefore described. It the oil afterr addition .ofallrali solution.kand agitation with steam separatesintogclearuiater and clear .oihitindicates that it Willnotbe benefited by kor requires no,Washinqf.,ok il M Alfter, anoill has been suitably Washed prior to acid treatment by;anyoithe preced` ing described 4methods .`respectingsour oil.

the sour` oil .resulting ti'ornk its` subsequent acid, treatment :is`vgenerally 'suitably Washed f it merely neutralized in the usual Way,lile a class 2 sourcils-.and the vsoaps remoyed by suitable dilutionwith agitation at suitable temperature: Though lthe sourcilis not .inclass -2,jits class'andmode of treatment -may bedeterininedasyhereinloetoi'e described in connection with sour oils iny general. ,f

- In` practicing; my method ofWashingV cils,"

it -Will be understood that kthe samples'awith soap and dilution.

y and iron etc areunsuitable for my'pn from pared Withthe batches oitoil to be "dashed in accordance with the deterinintionsjot tions. i i lThe predetermination of Quantity 'of soap` and ldegree of `dilution areoi? importance jromarenery standpoint in that attempts `to Wash largebatchesk otoil by agitation Vwith. soap or alkalnsolution Withoutpredetermination of dilution and quantity of' soap i or alkali solution.frequently will lead to eniulsication oit either the entire batch or a yF or example.y by my method 1500 barrels of the oil have been vWashed ina single operation.` while as little as k5 Vlitres or less of oil havesuiliiced for .making `the soap and dilution determinapartthereoi, andin consequence Will'in--.

Volve delay 'and expensive further treatnient, and in any event Willprobably result, ifthe oilis successfully separated troni the emulsion,in"leaving` thatoil oi emulsitying; character.

For thesake oi' brevity in the appended ,or hydroxide of an alkali metallor of ain- -ifnoniuin7 or ay carbonate or bicarbon t liere- .0155 orequivalent it being understooc` that Watersoluble soaps such as contain'calo i f Vllhat l claim is:

l. The method of treating oil, as

petroleurn'or petroleum product5 which consistsin Washingfthe same withsoap solun f tion, sr-nparating4 the Washed oil from the 'acbothasphaltic and non-asphaltic crude oilsj companying aqueous solution.acid.-treatingw angadueoussolution ofl alkali. Y

2. The method oit treating? mineral oil., as

ico`

petroleum orpetroleum'product which consists inwashino' the same Witn asolution containing; such Quantities oi? soap and Water as Will Wash`said oil Without substantial emulsiication Vthereof., separating 'thevWashed oil trom t e acccropanyingv aqueous solution, acid treating' theseparated cih separating; the resultant sludge and oil from each other,and thereafter neutraliriiigsaid y accompanying aqueous solutionyaeidtreat-v ing' theseparated oil7 separating the resultf iio :uit sludgeand oil from each other, and thereafter Washing said last named oil inthe presence of soap and Water in such quantities as preventemulsilication.

The method ot treating mineral oil, as

` petroleum or petroleum product, which comprises trashing the same withsoapr solution, separating they Washed oil 'from the accompenyingaqueous solution, recovering the soap materials from said aqueoussolution, and employing said soap materials for Washing mineral oil.

The method oit treating mineral oil, as petroleum or petroleum product,which comprises adding soap forming acids to said oil, agitating saidoil and acids with an aqueous alkaline solution, separating theresulting oil and aqueous emulsion. acidifying said aqueous emulsion,separating the resulting oil and soap forming acids and aqueoussolution, and adding the oil and soap forming acids to an oil to beWashed.

6. rihe method ot treating mineral oil, as petroleum or petroleumproduct, which consists in adding soap forming organic acids to saidoil,agitating said oil With alkaline solution, separating the resultinglaqueous solution and washed oil, treating said oil with acid, separatingthe resulting sludge and oil., neutraliaing` said oil with alkalinesolution, separating the resulting oil and aqueous solution, acidifyingsaid last named aqueous solution, separating the resulting oil andorganic soap forming acids from aqueous solution, and adding` saidseparated oil and acids to mi1 eral. oil to be Washed.

7. The method ot determining Whether an oil, as petroleum or petroleumproduct. contains the correctquantity or more or less of soap formingacids to torm with added alkali the. quantity of soap suitable for reemoving from the oil Without substantial emulsification thereof itsemulsilication inducing contents, which consists in adding to said oilallfali solution slightly in excess of said soap rorming acid, agitatingthe mixture` allowing the mixture to stand, and observing Whether thereis Vtirst. a clear separation of oil and aqueous solution, second, noseparation or separation intoa layer of emulsion and aqueous solution,or separation into layers of oil, emulsion and aqueous solnion` theemulsions in each instance'being immiscible with water. and third. noseparation or separation into layers of oil `and emulsion, the emulsionin each instance being miscible with Water.

F3. The method ot determining the dilution of soap solution suitable'for removing from oil, as petgoleiunor petroleum product, its

emulsification inducing contents Without sub-V the Washed Wax-free oil.

a gitating said samples, allowing said lsamples lto stand, and observingamongthe samples the sample or samples in which there is a clearseparation of oil and solution.

9. The method which consists in agitating troleum product, for removingtheretromf emulsicatlon Vinduclng contents Without substantialemulsilication of said oil, Which consists in adding differentquantities of soap solution to several samples of said oil, agitatingsaid samples, allowing the samples to stand, and observing among thesamples in Which there is a clear separation of oil and solution thatsample to which was added the smallest quantity of soap solution.

11. The method of treating crude petroleum, Which consists in toppingthe same, and Washing the resulting reduced crude oil With aqueous soapsolution.

12, The method of treating crude lpetroleum, which .consists in'steamreducing said crude petroleum, Washing and resulting reduced crude oilwith aqueous soap solution, and disti'lling the resulting Washed oil.

13. The method'ot treating reduced crude oil, which consists in Washingsaid oil with aqueous soap solution, acid treating said oil, Washingsaid acid treated Oil with an alkaline solution, and subjecting said oilto fractional distillation.

14. Themethod of treating reduced crude oil, which comprisesacid-treating the same, neutralizing the sour oil, distilling theneutralized oil, and Washing with soap solution an oil resulting'tromsaid distillation.

15. The method of treating reduced crude oil, which comprisesacid-treating thesame, neutralizing the sour oil, distilling the .neu-vtralized oil, Washing with soap solution an oil resulting from suchdistillation, and thereafter acid-treating the same.

16. The method of treating ivax'bearing oil, lWhich consists inseparating the Wax from the oil, Washing the Wax-free oilwit'h soapsolution, and thereafter acid-treating 17. The method of treatingmineral oil, as petroleum or petroleum product, which consists inwashing the same with soap solution, andthereafter acid-treating theWashed oil.

18. The method of treating mineral oil,

as petroleum or `petroleum product, which `comprises Washing the n oilwith soap solu-y tion, acid-treating the Washed oil, and there-k afterWashingk the acid-treatedoil With soap solution. Y

19. The method of treating mineral oil, as petroleum or petroleumproduct, Which comprises Washingthe oil with soap solution,acid-treating the Washed oil, and ',neui tralizing and Washing theresultant lsour oil,

20. The methody of treating mineral oil,v as petroleum or petroleumproduct, Which is p as petroleum r petroleum product, Which issubstantially free of sul'o-compounds of acid character and Whichcontains organic soap-forming acids linsulicient to form suffiu cientsoap for Washing the' oil, Which comprises neutralizing said organicacids While in the oil to form soaps, and thereaftery Washing the oilwith` an aqueous soap solu- `non-emulsi p l y i r 22. The method oftreating mineral oil, as

tion comprisingk said soaps and additional soap, the concentration andyquantity of said soap solution being such as to render the oil tying., iv

petroleum or petroleum product, Which comprises Washing the same Withsoapsolution, thereafter acid-treatinglthe Washed oil, and

thereafter Washing the sour oil With Water` and soap resulting fromneutralization of the organic acids in thesour oil.` i

23. The method of treating mineral oil, as'petroleum or petroleumproduct, Which comprises Washing the same with soap solution thereafteracid-treating thewashed oil,

'and thereafter Washing the sour oil With water and soap resulting fromneutralization of the organicl acids inthe sour eiland additional soap,the quantities of Water and totalsoap being such as to render theoil lnon-emulsifying.

' In testimony whereof I have hereunto axed my signature this 8th day ofMay7 1919.l t l nRNsT M. JoHANsEN.

